Catalyst composition, method of polymerization, and polymer therefrom

ABSTRACT

Catalyst compositions and methods, useful in polymerization processes, utilizing at least two metal compounds are disclosed. At least one of the metal compounds is a Group 15 containing metal compound and the other metal compound is preferably a bulky ligand metallocene-type catalyst. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

STATEMENT OF RELATED APPLICATIONS

The present application is a Continuation Application of U.S. Ser. No.09/865,067 filed May 24, 2001, now abandoned, which is a DivisionalApplication of, and claims priority to Ser. No. 09/425,387 filed Oct.22, 1999, now issued as U.S. Pat. No. 6,274,684.

FIELD OF THE INVENTION

The present invention relates to a catalyst composition comprising atleast two metal compounds useful in olefin polymerization processes toproduce polyolefins. Preferably, at least one of the metal compounds isa Group 15 containing metal compound. More preferably, the other metalcompound is a bulky ligand metallocene-type catalyst. The presentinvention also relates to a new polyolefin, generally polyethylene,particularly a multimodal polymer and more specifically, a bimodalpolymer, and its use in various end-use applications such as film,molding and pipe.

BACKGROUND OF THE INVENTION

Polyethylenes with a higher density and higher molecular weight arevalued in film applications requiring high stiffness, good toughness andhigh throughput. Such resins are also valued in pipe applicationsrequiring stiffness, toughness and long-term durability, andparticularly resistance to environmental stress cracking.

Typical metallocene polymerization catalysts (i.e. those containing atransition metal bound, for example, to at least one cyclopentadienyl,indenyl or fluorenyl group) have recently been used to produce resinshaving desirable product properties. While these resins have excellenttoughness properties, particularly dart impact properties, they, likeother metallocene catalyzed polyethylenes, can be difficult to process,for example, on older extrusion equipment. One of the means used toimprove the processing of such metallocene catalyzed polyethylenes is toblend them with another polyethylene. While the two polymer blend tendsto be more processable, it is expensive and adds a cumbersome blendingstep to the manufacturing/fabrication process.

Higher molecular weight confers desirable mechanical properties andstable bubble formation onto polyethylene polymers. However, it alsoinhibits extrusion processing by increasing backpressure in extruders,promotes melt fracture defects in the inflating bubble and potentially,promotes too high a degree of orientation in the finished film. Toremedy this, one may form a secondary, minor component of lowermolecular weight polymer to reduce extruder backpressure and inhibitmelt fracture. Several industrial processes operate on this principleusing multiple reactor technology to produce a processable bimodalmolecular weight distribution (MWD) high density polyethylene (HDPE)product. HIZEX™, a Mitsui Chemicals HDPE product, is considered theworldwide standard. HIZEX™ is produced in two or more reactors and iscostly to produce. In a multiple reactor process, each reactor producesa single component of the final product.

Others in the art have tried to produce two polymers together at thesame time in the same reactor using two different catalysts. PCT patentapplication WO 99/03899 discloses using a typical metallocene catalystand a conventional Ziegler-Natta catalyst in the same reactor to producea bimodal MWD HDPE. Using two different types of catalysts, however,result in a polymer whose characteristics cannot be predicted from thoseof the polymers that each catalyst would produce if utilized separately.This unpredictability occurs, for example, from competition or otherinfluence between the catalyst or catalyst systems used. These polymershowever still do not have a preferred balance of processability andstrength properties. Thus, there is a desire for a combination ofcatalysts capable of producing processable polyethylene polymers inpreferably a single reactor having desirable combinations of processing,mechanical and optical properties.

SUMMARY OF THE INVENTION

The present invention provides a catalyst composition, a polymerizationprocess using the catalyst composition, polymer produced therefrom andproducts made from the polymer.

In one embodiment, the invention is directed to a catalyst compositionincluding at least two metal compounds, where at least one metalcompound is a Group 15 containing metal compound, and where the othermetal compound is a bulky ligand metallocene-type compound, aconventional transition metal catalyst, or combinations thereof.

In one embodiment, the invention is directed to a catalyst compositionincluding at least two metal compounds, where at least one metalcompound is a Group 15 containing bidentate or tridentate ligated Group3 to 14 metal compound, preferably a Group 3 to 7, more preferably aGroup 4 to 6, and even more preferably a Group 4 metal compound, andwhere the other metal compound is a bulky ligand metallocene-typecompound, a conventional transition metal catalyst, or combinationsthereof. In this embodiment it is preferred that the other metalcompound is a bulky ligand metallocene-type compound.

In another embodiment, the invention is directed to a catalystcomposition including at least two metal compounds, where one metalcompound is a Group 3 to 14 metal atom bound to at least one leavinggroup and also bound to at least two Group 15 atoms, at least one ofwhich is also bound to a Group 15 or 16 atom through another group, andwhere the second metal compound, is different from the first metalcompound, and is a bulky ligand metallocene-type catalyst, aconventional-type transition metal catalyst, or combinations thereof.

In an embodiment, the invention is directed to processes forpolymerizing olefin(s) utilizing the above catalyst compositions,especially in a single polymerization reactor.

In yet another embodiment, the invention is directed to the polymersprepared utilizing the above catalyst composition, preferably to a newbimodal MWD HDPE.

DETAILED DESCRIPTION OF THE INVENTION Introduction

The present invention relates to the use of a mixed catalyst compositionwhere one of the catalysts is a Group 15 containing metal compound.Applicants have discovered that using these compounds in combinationwith another catalyst, preferably a bulky ligand metallocene typecompound, produces a new bimodal MWD HDPE product. Surprisingly, themixed catalyst composition of the present invention may be utilized in asingle reactor system.

Group 15 Containing Metal Compound

The mixed catalyst composition of the present invention includes a Group15 containing metal compound. The Group 15 containing compound generallyincludes a Group 3 to 14 metal atom, preferably a Group 3 to 7, morepreferably a Group 4 to 6, and even more preferably a Group 4 metalatom, bound to at least one leaving group and also bound to at least twoGroup 15 atoms, at least one of which is also bound to a Group 15 or 16atom through another group.

In one preferred embodiment, at least one of the Group 15 atoms is alsobound to a Group 15 or 16 atom through another group which may be a C₁to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom mayalso be bound to nothing or a hydrogen, a Group 14 atom containinggroup, a halogen, or a heteroatom containing group, and wherein each ofthe two Group 15 atoms are also bound to a cyclic group and mayoptionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

In a preferred embodiment, the Group 15 containing metal compound of thepresent invention may be represented by the formulae:

wherein

M is a Group 3 to 12 transition metal or a Group 13 or 14 main groupmetal, preferably a Group 4, 5, or 6 metal, and more preferably a Group4 metal, and most preferably zirconium, titanium or hafnium,

each X is independently a leaving group, preferably, an anionic leavinggroup, and more preferably hydrogen, a hydrocarbyl group, a heteroatomor a halogen, and most preferably an alkyl.

y is 0 or 1 (when y is 0 group L′ is absent),

n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

m is the formal charge of the YZL or the YZL′ ligand, preferably 0, −1,−2 or −3, and more preferably −2,

L is a Group 15 or 16 element, preferably nitrogen,

L′ is a Group 15 or 16 element or Group 14 containing group, preferablycarbon, silicon or germanium,

Y is a Group 15 element, preferably nitrogen or phosphorus, and morepreferably nitrogen,

Z is a Group 15 element, preferably nitrogen or phosphorus, and morepreferably nitrogen,

R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a heteroatomcontaining group having up to twenty carbon atoms, silicon, germanium,tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, aryl or aralkylgroup, more preferably a linear, branched or cyclic C₂ to C₂₀ alkylgroup, most preferably a C₂ to C₆ hydrocarbon group.

R³ is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatomcontaining group, preferably a linear, cyclic or branched alkyl grouphaving 1 to 20 carbon atoms, more preferably R³ is absent, hydrogen oran alkyl group, and most preferably hydrogen

R⁴ and R⁵ are independently an alkyl group, an aryl group, substitutedaryl group, a cyclic alkyl group, a substituted cyclic alkyl group, acyclic aralkyl group, a substituted cyclic aralkyl group or multiplering system, preferably having up to 20 carbon atoms, more preferablybetween 3 and 10 carbon atoms, and even more preferably a C₁ to C₂₀hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkyl group,or a heteroatom containing group, for example PR₃, where R is an alkylgroup,

R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵ may beinterconnected to each other,

R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.

By “formal charge of the YZL or YZL′ ligand”, it is meant the charge ofthe entire ligand absent the metal and the leaving groups X.

By “R¹ and R² may also be interconnected” it is meant that R¹ and R² maybe directly bound to each other or may be bound to each other throughother groups. By “R⁴ and R⁵ may also be interconnected” it is meant thatR⁴ and R⁵ may be directly bound to each other or may be bound to eachother through other groups.

An alkyl group may be a linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

wherein

R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkyl group, ahalide, a heteroatom, a heteroatom containing group containing up to 40carbon atoms, preferably a C₁ to C₂₀ linear or branched alkyl group,preferably a methyl, ethyl, propyl or butyl group, any two R groups mayform a cyclic group and/or a heterocyclic group. The cyclic groups maybe aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² are independentlya methyl, ethyl, propyl or butyl group (including all isomers), in apreferred embodiment R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹are hydrogen.

In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

In this embodiment, M is a Group 4 metal, preferably zirconium, titaniumor hafnium, and even more preferably zirconium; each of L, Y, and Z isnitrogen; each of R¹ and R² is —CH₂—CH₂—; R³ is hydrogen; and R⁶ and R⁷are absent.

In a particularly preferred embodiment the Group 15 containing metalcompound is represented by the formula:

In compound I, Ph equals phenyl.

The Group 15 containing metal compounds of the invention are prepared bymethods known in the art, such as those disclosed in EP 0 893 454 A1,U.S. Pat. No. 5,889,128 and the references cited in U.S. Pat. No.5,889,128 which are all herein incorporated by reference. U.S.application Ser. No. 09/312,878, filed May 17, 1999, discloses a gas orslurry phase polymerization process using a supported bisamide catalyst,which is also incorporated herein by reference.

A preferred direct synthesis of these compounds comprises reacting theneutral ligand, (see for example YZL or YZL′ of formula 1 or 2) withM^(n)X_(n) (M is a Group 3 to 14 metal, n is the oxidation state of M,each X is an anionic group, such as halide, in a non-coordinating orweakly coordinating solvent, such as ether, toluene, xylene, benzene,methylene chloride, and/or hexane or other solvent having a boilingpoint above 60° C., at about 20 to about 150° C. (preferably 20 to 100°C.), preferably for 24 hours or more, then treating the mixture with anexcess (such as four or more equivalents) of an alkylating agent, suchas methyl magnesium bromide in ether. The magnesium salts are removed byfiltration, and the metal complex isolated by standard techniques.

In one embodiment the Group 15 containing metal compound is prepared bya method comprising reacting a neutral ligand, (see for example YZL orYZL′ of formula 1 or 2) with a compound represented by the formulaM^(n)X_(n) (where M is a Group 3 to 14 metal, n is the oxidation stateof M, each X is an anionic leaving group) in a non-coordinating orweakly coordinating solvent, at about 20° C. or above, preferably atabout 20 to about 100° C., then treating the mixture with an excess ofan alkylating agent, then recovering the metal complex. In a preferredembodiment the solvent has a boiling point above 60° C., such astoluene, xylene, benzene, and/or hexane. In another embodiment thesolvent comprises ether and/or methylene chloride, either beingpreferable.

Bulky Ligand Metallocene-Type Compound

In addition to the Group 15 containing metal compound, the mixedcatalyst composition of the present invention also includes a secondmetal compound, which is preferably a bulky ligand metallocene-typecompound.

Generally, bulky ligand metallocene-type compounds include half and fullsandwich compounds having one or more bulky ligands bonded to at leastone metal atom. Typical bulky ligand metallocene-type compounds aregenerally described as containing one or more bulky ligand(s) and one ormore leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligands is η-bonded to themetal atom, most preferably η⁵-bonded to the metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare represented by the formula:L^(A)L^(B)MQ_(n)  (III)

where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)and are any ancillary ligand system, including unsubstituted orsubstituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands,heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (III) only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluroethyl,difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted pnictogenradicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, chalcogen radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Non-hydrogensubstituents R include the atoms carbon, silicon, boron, aluminum,nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like,including olefins such as but not limited to olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example but-3-enyl,prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups,preferably two adjacent R groups, are joined to form a ring structurehaving from 3 to 30 atoms selected from carbon, nitrogen, oxygen,phosphorous, silicon, germanium, aluminum, boron or a combinationthereof. Also, a substituent group R group such as 1-butanyl may form acarbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. In one embodiment, Q is a monoanionic labile ligand having asigma-bond to M. Depending on the oxidation state of the metal, thevalue for n is 0, 1 or 2 such that formula (III) above represents aneutral bulky ligand metallocene-type catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsof the invention include those of formula (III) where L^(A) and L^(B)are bridged to each other by at least one bridging group, A, such thatthe formula is represented byL^(A)AL^(B)MQ_(n)  (IV)

These bridged compounds represented by formula (IV) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (IV) have two or morebridging groups A (EP 664 301 B1).

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare those where the R substituents on the bulky ligands L^(A) and L^(B)of formulas (III) and (IV) are substituted with the same or differentnumber of substituents on each of the bulky ligands. In anotherembodiment, the bulky ligands L^(A) and L^(B) of formulas (III) and (IV)are different from each other.

Other bulky ligand metallocene-type catalyst compounds and catalystsystems useful in the invention may include those described in U.S. Pat.Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

In one embodiment, bulky ligand metallocene-type catalysts compoundsuseful in the invention include bridged heteroatom, mono-bulky ligandmetallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

In this embodiment, the bulky ligand metallocene-type catalyst compoundis represented by the formula:L^(C)AJMQ_(n)  (V)

where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to M and J; J is a heteroatom ancillary ligand; and A isa bridging group; Q is a univalent anionic ligand; and n is the integer0, 1 or 2. In formula (V) above, L^(C), A and J form a fused ringsystem. In an embodiment, L^(C) of formula (V) is as defined above forL^(A), A, M and Q of formula (V) are as defined above in formula (III).

In formula (V) J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In an embodiment of the invention, the bulky ligand metallocene-typecatalyst compounds are heterocyclic ligand complexes where the bulkyligands, the ring(s) or ring system(s), include one or more heteroatomsor a combination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these bulky ligandmetallocene-type catalyst compounds are described in WO 96/33202, WO96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Pat.Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417,and 5,856,258 all of which are herein incorporated by reference.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare those complexes known as transition metal catalysts based onbidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

In a preferred embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

In a particularly preferred embodiment, the other metal compound orsecond metal compound is the bulky ligand metallocene-type catalystcompound is represented by the formula:L^(D)MQ₂(YZ)X_(n)  (VI)where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a ligand, preferably a unicharged polydentate ligand; Aor Q is a univalent anionic ligand also bonded to M; X is a univalentanionic group when n is 2 or X is a divalent anionic group when n is 1;n is 1 or 2.

In formula (VI), L and M are as defined above for formula (III). Q is asdefined above for formula (III), preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In a particularly preferred embodiment the bulky ligand metallocene-typecompound is represented by the formula:

Activator and Activation Methods

The metal compounds described herein are preferably combined with one ormore activators to form an olefin polymerization catalyst system.

For the purposes of this patent specification and appended claims, theterm “activator” is defined to be any compound or component or methodwhich can activate any of the Group 15 containing metal compounds and/orthe bulky ligand metallocene-type catalyst compounds of the invention asdescribed above. Non-limiting activators, for example may include aLewis acid or a non-coordinating ionic activator or ionizing activatoror any other compound including Lewis bases, aluminum alkyls,conventional-type cocatalysts and combinations thereof that can converta neutral bulky ligand metallocene-type catalyst compound or Group 15containing metal compound to a catalytically active Group 15 containingmetal compound or bulky ligand metallocene-type cation. It is within thescope of this invention to use alumoxane or modified alumoxane as anactivator, and/or to also use ionizing activators, neutral or ionic,such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, atrisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtylboron metalloid precursor, polyhalogenated heteroborane anions (WO98/43983) or combination thereof, that would ionize the neutral bulkyligand metallocene-type catalyst and/or the Group 15 containing metalcompound.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a Group 15containing metal compound cation or bulky ligand metallocene-typecatalyst cation and their non-coordinating anion are also contemplated,and are described in EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No.5,387,568, which are all herein incorporated by reference.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586,EP-A-0 594-218 and EP-B1-0 586 665, and PCT publication WO 94/10180, allof which are herein fully incorporated by reference.

Organoaluminum compounds useful as activators include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

Ionizing compounds may contain an active proton, or some other cationassociated with but not coordinated to or only loosely coordinated tothe remaining ion of the ionizing compound. Such compounds and the likeare described in European publications EP-A-0 570 982, EP-A-0 520 732,EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, andU.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025,5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380,filed Aug. 3, 1994, all of which are herein fully incorporated byreference.

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. WO 98/09996 incorporated herein by referencedescribes activating bulky ligand metallocene-type catalyst compoundswith perchlorates, periodates and iodates including their hydrates. WO98/30602 and WO 98/30603 incorporated by reference describe the use oflithium (2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for abulky ligand metallocene-type catalyst compound. WO 99/18135incorporated herein by reference describes the use oforgano-boron-aluminum acitivators. EP-B1-0 781 299 describes using asilylium salt in combination with a non-coordinating compatible anion.Also, methods of activation such as using radiation (see EP-B1-0 615 981herein incorporated by reference), electro-chemical oxidation, and thelike are also contemplated as activating methods for the purposes ofrendering the neutral bulky ligand metallocene-type catalyst compound orprecursor to a bulky ligand metallocene-type cation capable ofpolymerizing olefins. Other activators or methods for activating a bulkyligand metallocene-type catalyst compound are described in for example,U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

It is also within the scope of this invention that the above describedGroup 15 containing metal compounds and bulky ligand metallocene-typecatalyst compounds can be combined with one or more of the catalystcompounds represented by formulas (III) through (VI) with one or moreactivators or activation methods described above.

It is also contemplated that any one of the bulky ligandmetallocene-type catalyst compounds of the invention have at least onefluoride or fluorine containing leaving group as described in U.S.application Ser. No. 09/191,916 filed Nov. 13, 1998.

In a preferred embodiment modified alumoxanes are combined with thefirst and second metal compounds of the invention to form a catalystsystem. In a preferred embodiment MMAO3A (modified methyl alumoxane inheptane, commercially available from Akzo Chemicals, Inc., Holland,under the trade name Modified Methylalumoxane type 3A, see for examplethose aluminoxanes disclosed in U.S. Pat. No. 5,041,584, which is hereinincorporated by reference) is combined with the first and second metalcompounds to form a catalyst system.

The first and second metal compounds may be combined at molar ratios of1:1000 to 1000:1, preferably 1:99 to 99:1, preferably 10:90 to 90:10,more preferably 20:80 to 80:20, more preferably 30:70 to 70:30, morepreferably 40:60 to 60:40. The particular ratio chosen will depend onthe end product desired and/or the method of activation.

In a particular embodiment, when using, the metal compounds representedby Formula 1 and Formula 2, where both are activated with the sameactivator, the preferred weight percents, based upon the weight of thetwo metal compounds, but not the activator or any support, are 10 to 95weight % compound of formula 1 and 5 to 90 weight % compound of formula2, preferably 50 to 90 weight % compound of Formula 1 and 10 to 50weight % compound of formula 2, more preferably 60 to 80 weight %compound of formula 1 to 40 to 20 weight % compound of formula 2. In aparticularly preferred embodiment the compound of Formula 2 is activatedwith methylalumoxane, then combined with the compound of Formula 2, theninjected in the reactor.

In one particular embodiment, when using Compound I and indenylzirconium tris-pivalate where both are activated with the sameactivator, the preferred weight percents, based upon the weight of thetwo catalysts, but not the activator or any support, are 10 to 95 weight% Compound I and 5 to 90 weight % indenyl zirconium trispivalate,preferably 50 to 90 weight % Compound I and 10 to 50 weight % indenylzirconium tris-pivalate, more preferably 60-80 weight % Compound I to 40to 20 weight % indenyl zirconium tris-pivalate. In a particularlypreferred embodiment the indenyl zirconium tris-pivalate is activatedwith methylalumoxane, then combined with Compound I, then injected inthe reactor.

In general the combined metal compounds and the activator are combinedin ratios of about 1000:1 to about 0.5:1. In a preferred embodiment themetal compounds and the activator are combined in a ratio of about 300:1to about 1:1, preferably about 150:1 to about 1:1, for boranes, borates,aluminates, etc. the ratio is preferably about 1:1 to about 10:1 and foralkyl aluminum compounds (such as diethylaluminum chloride combined withwater) the ratio is preferably about 0.5:1 to about 10:1.

Conventional-Type Catalyst Systems Combinable with Formulae I and II

The mixed catalyst composition of the present invention may alternatelyinclude the Group 15 containing metal compound, as described above, anda conventional-type transition catalyst.

Conventional-type transition metal catalysts are those traditionalZiegler-Natta, vanadium and Phillips-type catalysts well known in theart. Such as, for example Ziegler-Natta catalysts as described inZiegler-Natta Catalysts and Polymerizations, John Boor, Academic Press,New York, 1979. Examples of conventional-type transition metal catalystsare also discussed in U.S. Pat. Nos. 4,115,639, 4,077,904, 4,482,687,4,564,605, 4,721,763, 4,879,359 and 4,960,741 all of which are hereinfully incorporated by reference. The conventional-type transition metalcatalyst compounds that may be used in the present invention includetransition metal compounds from Groups 3 to 17, preferably 4 to 12, morepreferably 4 to 6 of the Periodic Table of Elements.

These conventional-type transition metal catalysts may be represented bythe formula: MR_(x), where M is a metal from Groups 3 to 17, preferablyGroup 4 to 6, more preferably Group 4, most preferably titanium; R is ahalogen or a hydrocarbyloxy group; and x is the oxidation state of themetal M. Non-limiting examples of R include alkoxy, phenoxy, bromide,chloride and fluoride. Non-limiting examples of conventional-typetransition metal catalysts where M is titanium include TiCl₄, TiBr₄,Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl, Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂,TiCl₃.1/3AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036, hereinincorporated by reference, describes various conventional-type vanadiumcatalyst compounds. Non-limiting examples of conventional-type vanadiumcatalyst compounds include vanadyl trihalide, alkoxy halides andalkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

Conventional-type chromium catalyst compounds, often referred to asPhillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

Still other conventional-type transition metal catalyst compounds andcatalyst systems suitable for use in the present invention are disclosedin U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758,5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and 5,869,585 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all hereinincorporated by reference.

Other catalysts may include cationic catalysts such as AlCl₃, and othercobalt, iron, nickel and palladium catalysts well known in the art. Seefor example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and 4,689,437all of which are incorporated herein by reference.

Typically, these conventional-type transition metal catalyst compoundsexcluding some conventional-type chromium catalyst compounds areactivated with one or more of the conventional-type cocatalystsdescribed below. Also conventional type transition metal catalysts canbe activated using the activators described above in this patentspecification as appreciated by one in the art.

Conventional-type cocatalyst compounds for the above conventional-typetransition metal catalyst compounds may be represented by the formulaM³M⁴ _(v)X² _(c)R³ _(b−c), wherein M³ is a metal from Group 1 to 3 and12 to 13 of the Periodic Table of Elements; M⁴ is a metal of Group 1 ofthe Periodic Table of Elements; v is a number from 0 to 1; each X² isany halogen; c is a number from 0 to 3; each R³ is a monovalenthydrocarbon radical or hydrogen; b is a number from 1 to 4; and whereinb minus c is at least 1. Other conventional-type organometalliccocatalyst compounds for the above conventional-type transition metalcatalysts have the formula M³R³ _(k), where M³ is a Group IA, IIA, IIBor IIIA metal, such as lithium, sodium, beryllium, barium, boron,aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3 depending uponthe valency of M³ which valency in turn normally depends upon theparticular Group to which M³ belongs; and each R³ may be any monovalenthydrocarbon radical.

Non-limiting examples of conventional-type organometallic cocatalystcompounds useful with the conventional-type catalyst compounds describedabove include methyllithium, butyllithium, dihexylmercury,butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc,tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude monoorganohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

Polymerization Process

The metal compounds, mixed metal compounds and catalyst systemsdescribed above are suitable for use in any polymerization process,including solution, gas or slurry processes or a combination thereof.The polymerization process is preferably a gas or slurry phase processand more preferably utilizes a single reactor, and most preferably asingle gas phase reactor.

In a preferred embodiment, the catalyst system consists of the metalcompounds (catalyst) and or the activator (cocatalyst) which arepreferably introduced into the reactor in solution. Solutions of themetal compounds are prepared by taking the catalyst and dissolving it inany suitable solvent such as an alkane, toluene, xylene, etc. Thesolvent may first be purified in order to remove any poisons, which mayaffect the catalyst activity, including any trace water and/oroxygenated compounds. Purification of the solvent may be accomplished byusing activated alumina and activated supported copper catalyst. Thecatalyst is preferably completely dissolved into the solution to form ahomogeneous solution. Both catalysts may be dissolved into the samesolvent, if desired. Once the catalysts are in solution, they may bestored indefinitely until use.

For polymerization, it preferred that the catalyst is combined with anactivator prior to introduction into the reactor. Additionally, othersolvents and reactants can be added to the catalyst solutions (on-lineor off-line), to the activator (on-line or off-line), or to theactivated catalyst or catalysts. See U.S. Pat. Nos. 5,317,036 and5,693,727, EP-A-0 593 083, and WO 97/46599 which are fully incorporatedherein by reference, that describe solution feed systems to a reactor.There are many different configurations which are possible to combinethe catalysts and activator.

The catalyst system, the metal compounds and or the activator arepreferably introduced into the reactor in one or more solutions. Themetal compounds may be activated independently, in series or together.In one embodiment a solution of the two activated metal compounds in analkane such as pentane, hexane, toluene, isopentane or the like isintroduced into a gas phase or slurry phase reactor. In anotherembodiment the catalysts system or the components can be introduced intothe reactor in a suspension or an emulsion. In one embodiment, thesecond metal compound is contacted with the activator, such as modifiedmethylalumoxane, in a solvent and just before the solution is fed into agas, slurry or solution phase reactor. A solution of the Group 15containing metal compound is combined with a solution of the secondcompound and the activator and then introduced into the reactor.

In the following illustrations, A refers to a catalyst or mixture ofcatalysts, and B refers to a different catalyst or mixture of catalysts.The mixtures of catalysts in A and B can be the same catalysts, just indifferent ratios. Further, it is noted that additional solvents or inertgases may be added at many locations.

Illustration 1: A and B plus the activator are mixed off-line and thenfed to the reactor.

Illustration 2: A and B are mixed off-line. Activator is added in-lineand then fed to the reactor.

Illustration 3: A or B is contacted with the activator (off-line) andthen either A or B is added in-line before entering the reactor.

Illustration 4: A or B is contacted with the activator (on-line) andthen either A or B is added in-line before entering the reactor.

Illustration 5: A and B are each contacted with the activator off-line.Then A and activator and B and activator are contacted in line beforeentering the reactor.

Illustration 6: A and B are each contacted with the activator in-line.Then A and activator and B and activator are contacted in-line beforeentering the reactor. (This is a preferred configuration since the ratioof A to B and the ratio of activator to A and the ratio of activator toB can be controlled independently.)

Illustration 7: In this example, A or B is contacted with the activator(on-line) while a separate solution of either A or B is contacted withactivator off-line. Then both stream of A or B and activator arecontacted in-line before entering the reactor.

Illustration 8: A is contacted on-line with B. Then, an activator is fedto in-line to the A and B mixture.

Illustration 9: A is activated with activator off-line. Then A andactivator is contacted on-line with B. Then, an activator is fed toin-line to the A and B and activator mixture.

In one embodiment, this invention is directed toward the polymerizationor copolymerization reactions involving the polymerization of one ormore monomers having from 2 to 30 carbon atoms, preferably 2 to 12carbon atoms, and more preferably 2 to 8 carbon atoms. The invention isparticularly well suited to the copolymerization reactions involving thepolymerization of one or more olefin monomers of ethylene, propylene,butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1,3-methyl-pentene-1, 3,5,5-trimethyl-hexene-1 and cyclic olefins or acombination thereof. Other monomers can include vinyl monomers,diolefins such as dienes, polyenes, norbornene, norbornadiene monomers.Preferably a copolymer of ethylene is produced, where the comonomer isat least one alpha-olefin having from 4 to 15 carbon atoms, preferablyfrom 4 to 12 carbon atoms, more preferably from 4 to 8 carbon atoms andmost preferably from 4 to 7 carbon atoms. In an alternate embodiment,the geminally disubstituted olefins disclosed in WO 98/37109 may bepolymerized or copolymerized using the invention herein described.

In another embodiment ethylene or propylene is polymerized with at leasttwo different comonomers to form a terpolymer. The preferred comonomersare a combination of alpha-olefin monomers having 4 to 10 carbon atoms,more preferably 4 to 8 carbon atoms, optionally with at least one dienemonomer. The preferred terpolymers include the combinations such asethylene/butene-1/hexene-1, ethylene/propylene/butene-1,propylene/ethylene/hexene-1, ethylene/propylene/norbornene and the like.

In a particularly preferred embodiment the process of the inventionrelates to the polymerization of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms, preferably 4 to 7 carbon atoms.Particularly, the comonomers are butene-1, 4-methyl-pentene-1, hexene-1and octene-1, the most preferred being hexene-1 and/or butene-1.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228 allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 100 psig (690 kPa) to about 400 psig (2759 kPa), preferably in therange of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa),more preferably in the range of from about 250 psig (1724 kPa) to about350 psig (2414 kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 75° C. to 110° C., and mostpreferably in the range of from about 85° C. to about 110° C. Alteringthe polymerization temperature can also be used as a tool to alter thefinal polymer product properties.

The productivity of the catalyst or catalyst system is influenced by themain monomer partial pressure. The preferred mole percent of the mainmonomer, ethylene or propylene, preferably ethylene, is from about 25 to90 mole percent and the monomer partial pressure is in the range of fromabout 75 psia (517 kPa) to about 300 psia (2069 kPa), which are typicalconditions in a gas phase polymerization process. In one embodiment theethylene partial pressure is about 220 to 240 psi (1517-1653 kPa). Inanother embodiment the molar ratio of hexene to ethylene ins the reactoris 0.03:1 to 0.08:1.

In a preferred embodiment, the reactor utilized in the present inventionand the process of the invention produce greater than 500 lbs of polymerper hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher ofpolymer, preferably greater than 1000 lbs/hr (455 Kg/hr), morepreferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferablygreater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greaterthan 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greaterthan 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst as a solution, as a suspension, as anemulsion, as a slurry in isobutane or as a dry free flowing powder isinjected regularly to the reactor loop, which is itself filled withcirculating slurry of growing polymer particles in a diluent ofisobutane containing monomer and comonomer. Hydrogen, optionally, may beadded as a molecular weight control. The reactor is maintained atpressure of about 525 psig to 625 psig (3620 kPa to 4309 kPa) and at atemperature in the range of about 140° F. to about 220° F. (about 60° C.to about 104° C.) depending on the desired polymer density. Reactionheat is removed through the loop wall since much of the reactor is inthe form of a double-jacketed pipe. The slurry is allowed to exit thereactor at regular intervals or continuously to a heated low pressureflash vessel, rotary dryer and a nitrogen purge column in sequence forremoval of the isobutane diluent and all unreacted monomer andcomonomers. The resulting hydrocarbon free powder is then compounded foruse in various applications.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of ethylene in the reactor liquid medium is in the rangeof from about 1 to 10 weight percent, preferably from about 2 to about 7weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent.

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This preferred process is describedin PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352, which areherein fully incorporated by reference.

In a preferred embodiment of the invention, a slurry of an aluminumdistearate in mineral oil is introduced into the reactor, separately orwith the first and or second metal complex and/or with an activator,from the metal compounds and or the activators. More information onusing aluminum stearate type additives may be found in U.S. applicationSer. No. 09/113,261 filed Jul. 10, 1998, which is incorporated byreference herein.

In an embodiment, if the second metal compound and Group 15 metalcompound of the catalyst system are introduced to the reactor in series,it is preferably that the second metal compound is added and/oractivated first and that the Group 15 metal compound is added and/oractivated second.

In another embodiment, the residence time of the catalyst composition isbetween about 3 to about 6 hours and preferably between about 3.5 andabout 5 hours.

In an embodiment, the mole ratio of comonomer to ethylene, C_(x)/C₂,where C_(x) is the amount of comonomer and C₂ is the amount of ethyleneis between about 0.001 to 0.0100 and more preferably between about 0.002to 0.008.

The melt index (and other properties) of the polymer produced may bechanged by manipulating hydrogen concentration in the polymerizationsystem by:

-   -   1.) changing the amount of the first catalyst in the        polymerization system, and/or    -   2.) changing the amount of the second catalyst in the        polymerization system, and/or    -   3.) adding hydrogen to the polymerization process; and/or    -   4.) changing the amount of liquid and/or gas that is withdrawn        and/or purged from the process; and/or    -   5.) changing the amount and/or composition of a recovered liquid        and/or recovered gas returned to the polymerization process,        said recovered liquid or recovered gas being recovered from        polymer discharged from the polymerization process; and/or    -   6.) using a hydrogenation catalyst in the polymerization        process; and/or    -   7.) changing the polymerization temperature; and/or    -   8.) changing the ethylene partial pressure in the polymerization        process; and/or    -   9.) changing the ethylene to hexene ratio in the polymerization        process; and/or    -   10.) changing the activator to transition metal ratio in the        activation sequence.

The hydrogen concentration in the reactor is about 100 to 5000 ppm,preferably 200 to 2000 ppm, more preferably 250 to 1900 ppm, morepreferably 300 to 1800 ppm, and more preferably 350 to 1700 ppm, morepreferably 400 to 1600 ppm, more preferably 500 to 1500 ppm, morepreferably 500 to 1400 ppm, more preferably 500 to 1200 ppm, morepreferably 600 to 1200 ppm, preferably 700 to 1100 ppm, and morepreferably 800 to 1000 ppm. The hydrogen concentration in the reactorbeing inversely proportional to the polymer's weight average molecularweight (M_(W)).

The catalyst and/or the activator may be placed on, deposited on,contacted with, incorporated within, adsorbed, or absorbed in a support.Typically the support is any of the solid, porous supports, includingmicroporous supports. Typical support materials include talc; inorganicoxides such as silica, magnesium chloride, alumina, silica-alumina;polymeric supports such as polyethylene, polypropylene, polystyrene,cross-linked polystyrene; and the like. Preferably the support is usedin finely divided form. Prior to use the support is preferably partiallyor completely dehydrated. The dehydration may be done physically bycalcining or by chemically converting all or part of the activehydroxyls. For more information on how to support catalysts, see U.S.Pat. No. 4,808,561 which discloses how to support a metallocene catalystsystem. In addition, there are various other techniques of supportingcatalysts as are well known in the art. Methods for supporting the Group15 metal compound of the invention are described in U.S. applicationSer. No. 09/312,878, filed May 17, 1999 which is herein incorporated byreference.

Polymer of the Invention

The new polymers produced by the process of the present invention may beused in a wide variety of products and end use applications. Preferablythe new polymers include polyethylene, and even more preferably includebimodal polyethylene produced in a single reactor. In addition tobimodal polymers, it is not beyond the scope of the present applicationto produce a unimodal or multi-modal polymer.

The Group 15 containing metal compound, when used alone, produces a highweight average molecular weight M_(w) polymer (such as for example above100,000, preferably above 150,000, preferably above 200,000, preferablyabove 250,000, more preferably above 300,000). The second metalcompound, when used alone, produces a low molecular weight polymer (suchas for example below 80,000, preferably below 70,000, preferably below60,000, more preferably below 50,000, more preferably below 40,000, morepreferably below 30,000, more preferably below 20,000 and above 5,000,more preferably below 20,000 and above 10,000).

The polyolefins, particularly polyethylenes, produced by the presentinvention, have a density of 0.89 to 0.97 g/cm³. Preferably,polyethylenes having a density of 0.910 to 0.965 g/cm³, more preferably0.915 to 0.960 g/cm³, and even more preferably 0.920 to 0.955 g/cm³ canbe produced. In some embodiments, a density of 0.915 to 0.940 g/cm³would be preferred, in other embodiments densities of 0.930 to 0.970g/cm³ are preferred.

In a preferred embodiment, the polyolefin recovered typically has a meltindex I₂ (as measured by ASTM D-1238, Condition E at 190° C.) of about0.01 to 1000 dg/min or less. In a preferred embodiment, the polyolefinis ethylene homopolymer or copolymer. In a preferred embodiment forcertain applications, such as films, pipes, molded articles and thelike, a melt index of 10 dg/min or less is preferred. For some films andmolded articles, a melt index of 1 dg/min or less is preferred.Polyethylene having a I₂ between 0.01 and 10 dg/min is preferred.

In a preferred embodiment the polymer produced herein has an I₂₁ (asmeasured by ASTM-D-1238-F, at 190° C.) of 0.1 to 10 dg/min, preferably0.2 to 7.5 dg/min, preferably 2.0 dg/min or less, preferably 1.5 dg/minor less, preferably 1.2 dg/min or less, more preferably between 0.5 and1.0 dg/min, more preferably between 0.6 and 0.8 dg/min.

In another embodiment, the polymers of the invention have a melt flowindex “MIR” of I₂₁/I₂ of 80 or more, preferably 90 or more, preferably100 or more, preferably 125 or more.

In another embodiment the polymer has an I₂₁ (as measured by ASTM 1238,condition F, at 190° C.)(sometimes referred to as Flow Index) of 2.0dg/min or less, preferably 1.5 dg/min or less, preferably 1.2 dg/min orless, more preferably between 0.5 and 1.0 dg/min, more preferablybetween 0.6 and 0.8 dg/min and an I₂₁/I₂ of 80 or more, preferably 90 ormore, preferably 100 or more, preferably 125 or more and has one or moreof the following properties in addition:

-   -   (a) Mw/Mn of between 15 and 80, preferably between 20 and 60,        preferably between 20 and 40. Molecular weight (Mw and Mn) are        measured as described below in the examples section;    -   (b) an Mw of 180,000 or more, preferably 200,000 or more,        preferably 250,000 or more, preferably 300,000 or more;    -   (c) a density (as measured by ASTM 2839) of 0.94 to 0.970 g/cm³;        preferably 0.945 to 0.965 g/cm³; preferably 0.950 to 0.960        g/cm³;    -   (d) a residual metal content of 5.0 ppm transition metal or        less, preferably 2.0 ppm transition metal or less, preferably        1.8 ppm transition metal or less, preferably 1.6 ppm transition        metal or less, preferably 1.5 ppm transition metal or less,        preferably 2.0 ppm or less of Group 4 metal, preferably 1.8 ppm        or less of Group 4 metal, preferably 1.6 ppm or less of Group 4        metal, preferably 1.5 ppm or less of Group 4 metal, preferably        2.0 ppm or less zirconium, preferably 1.8 ppm or less zirconium,        preferably 1.6 ppm or less zirconium, preferably 1.5 ppm or less        zirconium(as measured by Inductively Coupled Plasma Optical        Emission Spectroscopy (ICPAES) run against commercially        available standards, where the sample is heated so as to fully        decompose all organics and the solvent comprises nitric acid        and, if any support is present, another acid to dissolve any        support (such as hydrofluoric acid to dissolve silica supports)        is present;    -   (e) 35 weight percent or more high weight average molecular        weight component, as measured by size-exclusion chromatography,        preferably 40% or more. In a particularly preferred embodiment        the higher molecular weight fraction is present at between 35        and 70 weight %, more preferably between 40 and 60 weight %.

In a preferred embodiment the catalyst composition described above isused to make a polyethylene having a density of between 0.94 and 0.970g/cm³ (as measured by ASTM D 2839) and an I₂ of 0.5 or less g/10 min orless

In another embodiment the catalyst composition described above is usedto make a polyethylene having an I₂₁ of less than 10 and a density ofbetween about 0.940 and 0.950 g/cm³ or an I₂₁ of less than 20 and adensity of about 0.945 g/cm³ or less.

In another embodiment, the polymer of the invention is made into a pipeby methods known in the art. For pipe applications, the polymers of theinvention have a I₂₁ of from about 2 to about 10 dg/min and preferablyfrom about 2 to about 8 dg/min. In another embodiment, the pipe of theinvention satisfies ISO qualifications.

In another embodiment, the catalyst composition of the present inventionis used to make polyethylene pipe able to withstand at least 50 years atan ambient temperature of 20° C., using water as the internal testmedium and either water or air as the outside environment (Hydro static(hoop) stress as measured by ISO TR 9080).

In another embodiment, the polymer has a notch tensile test (resistanceto slow crack growth) result of greater than 150 hours at 3.0 MPa,preferably greater than 500 hours at 3.0 MPa and more preferably greaterthan 600 hours at 3.0 mPa. (as measured by ASTM-F1473).

In another embodiment, the catalyst composition of the present inventionis used to make polyethylene pipe having a predicted S-4 T_(c) for 110mm pipe of less than −5° C., preferably of less than −15° C. and morepreferably less than −40° C. (ISO DIS 13477/ASTM F1589).

In another embodiment, the polymer has an extrusion rate of greater thanabout 17 lbs/hour/inch of die circumference and preferably greater thanabout 20 lbs/hour/inch of die circumference and more preferably greaterthan about 22 lbs/hour/inch of die circumference.

The polyolefins of the invention can be made into films, molded articles(including pipes), sheets, wire and cable coating and the like. Thefilms may be formed by any of the conventional techniques known in theart including extrusion, co-extrusion, lamination, blowing and casting.The film may be obtained by the flat film or tubular process which maybe followed by orientation in a uniaxial direction or in two mutuallyperpendicular directions in the plane of the film to the same ordifferent extents. Orientation may be to the same extent in bothdirections or may be to different extents. Particularly preferredmethods to form the polymers into films include extrusion or coextrusionon a blown or cast film line.

In another embodiment, the polymer of the invention is made into a filmby methods known in the art. For film application, the polymers of theinvention have a I₂₁ of from about 2 to about 50 dg/min, preferably fromabout 2 to about 30 dg/min, even more preferably from about 2 to about20 dg/min, still more preferably about 5 to about 15 dg/min and yet morepreferably from about 5 to about 10 dg/min.

In another embodiment, the polymer has an MD Tear of 0.5 mil (13μ) filmof between about 5 g/mil and 25 g/mil preferably, between about 15 g/miland 25 g/mil, and more preferably between about 20 g/mil and 25 g/mil.

The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins,hydrocarbon resins, glass beads and the like. The additives may bepresent in the typically effective amounts well known in the art, suchas 0.001 weight % to 10 weight %.

In another embodiment, the polymer of the invention is made into amolded article by methods known in the art, for example, by blow moldingand injection-stretch molding. For molded applications, the polymers ofthe invention have a I₂₁ of from about 20 dg/min to about 50 dg/min andpreferably from about 35 dg/min to about 45 dg/min.

In another embodiment, the polymers of the invention, including thosedescribed above, have an ash content less than 100 ppm, more preferablyless than 75 ppm, and even more preferably less than 50 ppm is produced.In another embodiment, the ash contains negligibly small levels oftitanium as measured by Inductively Coupled Plasma/Atomic EmissionSpectroscopy (ICPAES) as is well known in the art.

In another embodiment, the polymers of the invention, contain a nitrogencontaining ligand detectable by High Resolution Mass Spectroscopy (HRMS)as is well known in the art.

EXAMPLES

In order to provide a better understanding of the present invention,including representative advantages thereof, the following examples areoffered.

M_(n) and M_(w) were measured by gel permeation chromatography on awaters 150° C. GPC instrument equipped with differential refractionindex detectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer in question.

MWD=M_(w)/M_(n).

Density was measured according to ASTM D 1505.

Melt Index (MI) I₂ was measured according to ASTM D-1238, Condition E,at 190° C.

I₂₁ was measured according to ASTM D-1238, Condition F, at 190° C.

Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂.

Weight % comonomer was measured by proton NMR.

Dart Impact was measured according to ASTM D 1709.

MD and TD Elmendorf Tear were measured according to ASTM D 1922.

MD and TD 1% Secant modulus were measured according to ASTM D 882.

MD and TD tensile strength and ultimate tensile strength were measuredaccording to ASTM D 882.

MD and TD elongation and ultimate elongation were measured according toASTM D 412.

MD and TD Modulus were measured according to ASTM 882-91.

Haze was measured according to ASTM 1003-95, Condition A.

45° gloss was measured according to ASTM D 2457.

BUR is blow up ratio.

“PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw” isparts per million by weight.

Indenyl zirconium tris pivalate, a bulky ligand metallocene-typecompound, also represented by formula VI, can be prepared by performingthe following general reactions:

-   -   (1) Zr(NEt₂)₄+IndH→IndZr(NEt₂)₃+Et₂NH    -   (2) IndZr(NEt₂)₃+3(CH₃)₃CCO₂H→IndZr[O₂CC(CH₃)]₃+Et₂NH        Where Ind=indenyl and Et is ethyl.

Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]₂NH ligand (Ligand I)

A 2 L one-armed Schlenk flask was charged with a magnetic stir bar,diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51 g,0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14 mmol),racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemic BINAP)(2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol), andtoluene (800 mL) under dry, oxygen-free nitrogen. The reaction mixturewas stirred and heated to 100° C. After 18 h the reaction was complete,as judged by proton NMR spectroscopy. All remaining manipulations can beperformed in air. All solvent was removed under vacuum and the residuesdissolved in diethyl ether (1 L). The ether was washed with water (3×250mL) followed by saturated aqueous NaCl (180 g in 500 mL) and dried overmagnesium sulfate (30 g). Removal of the ether in vacuo yielded a redoil which was dried at 70° C. for 12 h under vacuum (yield: 71.10 g,92%). ¹H NMR (C₆D₆) δ 6.83 (s, 4), 3.39 (br s, 2), 2.86 (t, 4), 2.49 (t,4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).

Preparation of Catalyst A Preparation of 1.5 wt % Catalyst A in TolueneSolution

Note: All procedures below were performed in a glove box.

-   -   1.) Weighed out 100 grams of purified toluene into a 1 L        Erlenmeyer flask equipped with a Teflon coated stir bar.    -   2.) Added 7.28 grams of Tetrabenzyl Zirconium.    -   3.) Placed solution on agitator and stirred for 5 minutes. All        of the solids went into solution.    -   4.) Added 5.42 grams of Ligand I.    -   5.) Added an additional 551 grams of purified toluene and        allowed mixture to stir for 15 minutes. No solids remained in        the solution.    -   6.) Poured catalyst solution into a clean, purged 1-L Whitey        sample cylinder, labeled, removed from glovebox and placed in        holding area for operations.

Alternate Preparation of Compound I{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Zr(CH₂Ph)₂

A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and300 mL of toluene under dry, oxygen-free nitrogen. Solid ligand I above(32.773 g, 96.52 mmol) was added with stirring over 1 minute (thedesired compound precipitates). The volume of the slurry was reduced to100 mL and 300 mL of pentane added with stirring. The solidyellow-orange product was collected by filtration and dried under vacuum(44.811 g, 80% yield).

¹H NMR (C₆D₆) δ 7.22-6.81 (m, 12), 5.90 (d, 2), 3.38 (m, 2), 3.11 (m,2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41 (s, 6), 2.18 (s, 6),1.89 (s, 2), 0.96 (s, 2).

Preparation of Catalyst B Preparation 1 wt % Catalyst B in HexaneSolution

All procedures were performed in a glove box.

-   -   1.) Transfer 1 liter of purified hexane into a 1 L Erlenmeyer        flask equipped with a Teflon coated stir bar.    -   2.) Add 6.67 grams of indenyl zirconium tris pivalate dried        powder.    -   3.) Place solution on magnetic agitator and stir for 15 minutes.        All of the solids go into solution.    -   4.) Pour solution into a clean, purged 1-L Whitey sample        cylinder, labeled, and removed from glovebox and place in        holding area until use in operation.

Comparative Example 1

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 85° C. and 350 psig (2.4 MPa)total reactor pressure having a water cooled heat exchanger Ethylene wasfed to the reactor at a rate of about 40 pounds per hour (18.1 kg/hr),hexene was fed to the reactor at a rate of about 0.6 pounds per hour(0.27 kg/hr) and hydrogen was fed to the reactor at a rate of 5 mPPH.Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. Theproduction rate was about 27 PPH. The reactor was equipped with a plenumhaving about 1,900 PPH of recycle gas flow. (The plenum is a device usedto create a particle lean zone in a fluidized bed gas-phase reactor, asdescribed in detail in U.S. Pat. No. 5,693,727 which is incorporatedherein by reference.) A tapered catalyst injection nozzle having a 0.041inch (0.10 cm) hole size was positioned in the plenum gas flow. Asolution of 1 wt % of Catalyst A in toluene and cocatalyst (MMAO-3A, 1wt % Aluminum) were mixed in line prior to passing through the injectionnozzle into the fluidized bed. (MMAO-3A is modified methyl alumoxane inheptane, commercially available from Akzo Chemicals, Inc. under thetrade name Modified Methylalumoxane type 3A.) MMAO to catalyst wascontrolled so that the Al:Zr molar ratio was 400:1. Nitrogen andisopentane were also fed to the injection nozzle as needed to maintain astable average particle size. A unimodal polymer having nominal 0.28dg/min (I₂₁) and 0.935 g/cc (density) properties was obtained. Aresidual zirconium of 1.63 ppmw was calculated based on a reactor massbalance.

Comparative Example 2

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 80° C. and 320 psig (2.2 MPa)total reactor pressure having a water cooled heat exchanger Ethylene wasfed to the reactor at a rate of about 37 pounds per hour (19.8 kg/hr),hexene was fed to the reactor at a rate of about 0.4 pounds per hour(0.18 kg/hr) and hydrogen was fed to the reactor at a rate of 12 mPPH.Ethylene was fed to maintain 180 psi (1.2 MPa) ethylene partial pressurein the reactor. The production rate was about 25 PPH. The reactor wasequipped with a plenum having about 1,030 PPH of recycle gas flow. (Theplenum is a device used to create a particle lean zone in a fluidizedbed gas-phase reactor.) A tapered catalyst injection nozzle having a0.055 inch (0.14 cm) hole size was positioned in the plenum gas flow. Asolution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 40 minutes. In addition to the solution, isopentane andnitrogen were added to control particle size. The total system waspassed through the injection nozzle into the fluidized bed. MMAO tocatalyst ratio was controlled so that the Al:Zr molar ratio was 300:1. Abimodal polymer was produced which was 797 g/10 min melt index. Thedensity was 0.9678 g/cc. A residual zirconium of 0.7 ppmw was calculatedbased on a reactor mass balance. SEC analysis and deconvolution using 4floury distributions was completed and the results are shown in Table I.

Example 3

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 80° C. and 320 psig (2.2 MPa)total reactor pressure having a water cooled heat exchanger. Ethylenewas fed to the reactor at a rate of about 53 pounds per hour (24 kg/hr),hexene was fed to the reactor at a rate of about 0.5 pounds per hour(0.22 kg/hr) and hydrogen was fed to the reactor at a rate of 9 mPPH.Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partialpressure in the reactor. The production rate was about 25 PPH. Thereactor was equipped with a plenum having about 990 PPH of recycle gasflow. (The plenum is a device used to create a particle lean zone in afluidized bed gas-phase reactor.) A tapered catalyst injection nozzlehaving a 0.055 inch (0.12) hole size was positioned in the plenum gasflow. A solution of 1 wt % Catalyst B in hexane catalyst was mixed with0.2 lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 20-25 minutes. In a separate activating stainless steel tube,a 1 wt % Catalyst A in toluene solution was activated with cocatalyst(MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The twoindependently activated solutions were combined into a single processline for about 4 minutes. The quantity of Catalyst A catalyst was about40-45 mol % of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was300:1. A bimodal polymer was produced which was 0.045 g/10 min meltindex and 7.48 g/10 min flow index. The density was 0.9496 g/cc. Aresidual zirconium of 1.7 ppmw was calculated based on a reactor massbalance. SEC analysis and deconvolution using 7-8 floury distributionswas completed and the results are shown in Table I.

Example 4

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 85° C. and 320 psig (2.2 MPa)total reactor pressure having a water cooled heat exchanger. Ethylenewas fed to the reactor at a rate of about 50 pounds per hour (22.7kg/hr), some of the hexene was fed to the reactor at a rate of about 0.7pounds per hour (0.32 kg/hr) and hydrogen was fed to the reactor at arate of 11 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa)ethylene partial pressure in the reactor. The production rate was about29 PPH. The reactor was equipped with a plenum having about 970 PPH ofrecycle gas flow. (The plenum is a device used to create a particle leanzone in a fluidized bed gas-phase reactor.) A tapered catalyst injectionnozzle having a 0.055 inch (0.14 cm) hole size was positioned in theplenum gas flow. A solution of 1 wt % Catalyst B in hexane catalyst wasmixed with 0.2 lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch(0.48 cm) stainless steel tube for about 15 minutes. The Catalyst B andhexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) ina line for about 20-25 minutes. In a separate activating stainless steeltube, a 1 wt % Catalyst A in toluene solution was activated withcocatalyst (MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The twoindependently activated solutions were combined into a single processline for about 4 minutes. The quantity of Catalyst A catalyst was about40-45 mol % of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst was controlled so that the Al:Zr molar ratio was 300:1.A bimodal polymer was produced which was 0.054 g/10 min melt index and7.94 g/10 min flow index. The density was 0.948 g/cc. A residualzirconium of 1.1 ppmw was calculated based on a reactor mass balance.SEC analysis and deconvolution using 7-8 floury distributions wascompleted and the results are shown in Table I.

Example 5

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 85° C. and 320 psig (2.2 MPa)total reactor pressure having a water cooled heat exchanger Ethylene wasfed to the reactor at a rate of about 60 pounds per hour (27.2 kg/hr),hexene was fed to the reactor at a rate of about 0.8 pounds per hour(0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13 mPPH.Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partialpressure in the reactor. The production rate was about 34 PPH. Thereactor was equipped with a plenum having about 960 PPH of recycle gasflow. (The plenum is a device used to create a particle lean zone in afluidized bed gas-phase reactor.) A tapered catalyst injection nozzlehaving a 0.055 inch (0.14 cm) was positioned in the plenum gas flow. Asolution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 20-25 minutes. In a separate activating stainless steel tube,a 1 wt % Catalyst A in toluene solution was activated with cocatalyst(MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The twoindependently activated solutions were combined into a single processline for about 4 minutes. The quantity of Catalyst A catalyst was about40-45 mol % of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was300:1. A bimodal polymer was produced which was 0.077 g/10 min meltindex and 12.7 g/10 min flow index. The density was 0.9487 g/cc. Aresidual zirconium of 0.9 ppmw was calculated based on a reactor massbalance. SEC analysis and deconvolution using 7-8 floury distributionswas completed and the results are shown in Table I.

Example 6

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 85° C. and 320 psig (2.2 MPa)total reactor pressure having a water cooled heat exchanger. Ethylenewas fed to the reactor at a rate of about 60 pounds per hour (27.2kg/hr), hexene was fed to the reactor at a rate of about 0.8 pounds perhour (0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partialpressure in the reactor. The production rate was about 34 PPH. Thereactor was equipped with a plenum having about 1,100 PPH of recycle gasflow. (The plenum is a device used to create a particle lean zone in afluidized bed gas-phase reactor.) A tapered catalyst injection nozzlehaving a 0.055 inch (0.14 cm) was positioned in the plenum gas flow. Asolution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2lb/hr (0.09 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube for about 15 minutes. The Catalyst B and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a linefor about 10-15 minutes. 1 wt % Catalyst A in toluene solution was addedto the activated Catalyst B solution for about 5 minutes before beingsprayed into the reactor. The quantity of Catalyst A catalyst was about40-45 mol % of the total solution fed. In addition to the solution,isopentane and nitrogen were added to control particle size. The totalsystem was passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the final Al:Zr molarratio was 300:1. A bimodal polymer was produced which was 0.136 g/10 minmelt index and 38.1 g/10 min flow index. The density was 0.9488 g/cc. Aresidual zirconium of 0.5 ppmw was calculated based on a reactor massbalance. SEC analysis and deconvolution using 7-8 floury distributionswas completed and the results are shown in Table I.

Example 7

An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilotplant scale gas phase reactor operating at 85° C. and 350 psig (2.4 MPa)total reactor pressure having a water cooled heat exchanger. Ethylenewas fed to the reactor at a rate of about 42 pounds per hour (19.1kg/hr), hexene was fed to the reactor at a rate of about 0.8 pounds perhour (0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partialpressure in the reactor. The production rate was about 32 PPH. Thereactor was equipped with a plenum having about 2010 PPH of recycle gasflow. (The plenum is a device used to create a particle lean zone in afluidized bed gas-phase reactor.) A tapered catalyst injection nozzlehaving a 0.055 inch (0.14 cm) was positioned in the plenum gas flow. Asolution of 0.25 wt % Catalyst B in hexane catalyst was mixed with 0.1lb/hr (0.05 kg/hr) hexene in a {fraction (3/16)} inch (0.48 cm)stainless steel tube. The Catalyst B and hexene mixture were mixed withcocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 15 minutes.0.5 wt % Catalyst A in toluene solution was added to the activatedCatalyst B solution for about 15 minutes before being sprayed into thereactor. The quantity of Catalyst A catalyst was about 65-70 mol % ofthe total solution fed. In addition to the solution, isopentane andnitrogen were added to control particle size. The total system waspassed through the injection nozzle into the fluidized bed. MMAO tocatalyst ratio was controlled so that the final Al:Zr molar ratio was500. A bimodal polymer was produced which was 0.06 g/10 min melt indexand 6.26 g/10 min flow index. The density was 0.9501 g/cc. A residualzirconium of 0.65 ppmw was calculated based on a reactor mass balance.SEC analysis and deconvolution using 7-8 floury distributions wascompleted and the results are shown in Table I.

TABLE I Example 1 (Comp) 2 (Comp) 3 4 5 6 7 I₂₁ (dg/min) 0.28 n/a 7.57.94 12.6 38.1 6.26 I₂₁/I₂ — — 165.3 147 164.6 280.4 104 I₂ (dg/min) noflow 797 0.045 0.054 0.077 0.136 0.060 Experimental SEC Data Mn 80,6002,952 7,908 10,896 10,778 10,282 8,700 Mw 407,375 13,398 340,011 263,839259,389 261,138 287,961 Mw/Mn 5.05 4.54 43 24.2 24.1 25.4 33.10 Mn(calculated) — — 7,645 10,552 10,673 10,105 8,523 Mw (calculated) — —339,752 258,282 248,215 252,310 284,814 Mw/Mn (calculated) — — 44.4424.48 23.26 24.97 33.42 LMW Mn — 2,988 3,741 5,548 5,731 6,382 4,165(calculated) LMW Mw (calc.) — 13,214 13,259 16,388 15,214 18,333 11,771LMW Mw/Mn — 4.42 3.54 2.95 2.65 2.87 2.83 (calc.) HMW Mn 73,979 —122,758 111,256 85,461 88,374 115,954 (calculated) HMW Mw (calc.)407,513 — 633,154 501,013 484,657 607,625 526,630 HMW Mw/Mn 5.51 — 5.164.50 5.67 6.88 4.54 (calc.) SPLIT (HMW/Total) 100.00 0.00 52.67 49.9249.64 39.70 53.03 Reactor Conditions Reactor Temp (° C.) 85 80 80 85 8585 85 C₂ psi/Mpa 220/1.52 180/1.24 220/1.52 220/1.52 220/1.52 220/1.52220/1.52 H₂/C₂ mole ratio 0.0016 0.0018 0.0013 0.0014 0.0014 0.00100.0019 C₆/C₂ mole ratio 0.00488 0.00153 0.0074 0.0073 0.0077 0.00750.0050 Residence time (hr) 3.6 7.5 5.3 4.74 3.87 3.87 3.4 Molar ratio —— 0.71 0.73 0.76 0.76 2.16 HMW/LMW Molar % Catalyst A 100 — 41 42 43 4368 Zr ppm, by lab — — 1.33 1.61 1.33 0.8 0.97 Zr ppm, by feed 1.63 —1.46 1.06 0.9 0.54 0.62 Average 1.63 — 1.40 1.34 1.12 0.67 0.80 Al/Zrmole ratio 400 — 330 380 320 307 500 Catalyst B activity g — — 9,96512,515 18,754 37,288 50,142 PE/mmol cat-hr Catalyst A activity g 15,559— 15,730 17,042 24,323 32,465 26,203 PE/mmol cat-hr

Comparative Examples 1 and 2 give experimental data on how the singlecomponent catalyst system behave. Examples 3 and 4 demonstrate theeffect of temperature on essentially the same reactor conditions andcatalyst feed system. Note that at higher temperature, the M_(w)/M_(n)is lower, as is the MFR. Examples 5 and 6 compare the effect ofactivation scheme for essentially the same reactor conditions andcatalyst feed system. Note that in Example 6, the overall activity ofthe catalyst is better. However, the amount of high molecular weightmaterial produced is lower. Examples 6 and 7 demonstrate the ability tocontrol the amount of high molecular weight material produced atessentially similar reactor conditions. Example 7 fed a higherpercentage of Catalyst A feed, hence a higher quantity of higher Mwmaterial was produced.

Example 8

350 pounds (159 kg) of polyethylene produced according to example 4above (referred to as Polymer A) was compounded on a Werner-FleidererZSK-30 twin screw extruder with 1000 ppm Irganox™ 1076 and 1500 ppmIrgafos™ 1068 at a melt temperature of 220° C. and formed into pellets.Then the pellets were blown into a 0.5 mil (13 μm) film on an Alpineblown film extrusion line. The extrusion condition were: die-160 mmtriplex, 1.5 mm die gap, 400° C. die temperature, 48 inches (122 cm)layflat width, target melt temperature-410° F. (210° C.), and extrusionrates-310 lb/hr (144 kg/hr), 420 lb/hr (191 kg/hr) and 460 lb/hr (209kg/hr). ESCORENE™ HD7755.10 (a conventional series reactor product ofExxon Chemical Company, Houston, Tex.) was run at the same conditions asa comparison. All films were conditioned according to 23° C., 50%humidity for 40 hours. The data are reported in Table A.

TABLE A Polymer A HD7755.10 Polymer A HD7755.10 Polymer A HD7755.10 Ratelb/hr/ 317 (144) 317 (144) 421 (191) 421 (191) 460 (209) 460 (209)(kg/hr) Film Gage 0.524 mil/ 0.502 mil/ 0.532 mil/ 0.519 mil/ 0.543 mil/0.528 mil/ 13 μm 13 μm 14 μm 13 μm 14 μm 13 μm Density g/cc 0.9489 0.9490.9502 0.949 0.9468 0.9489 26″ (66 cm) 355 g 308 g 327 g 325 g nm nmdart @ 1 day 26″ (66 cm) 351 g 308 g 314 g 344 g 301 g 360 g dart @ 7days MD Tear 22 (0.87) 16 (0.63) 25 (0.98) 15 (0.59) 22 (0.87) 15 (0.59)g/mil (g/μ) TD Tear 97 (3.82) 102 (4.02) 77 (3.03) 84 (3.31) 100 (3.94)81 (3.19) g/mil (g/μ) 1% Secant 161,000 200,200 159,000 183,800 156,200178,700 MD, psi (MPa) (1110) (1380) (1096) (1267) (1077) (1232) 1%Secant 184,500 212,500 163,500 206,600 161,400 212,500 TD, psi (MPa)(1272) (1465) (1127) (1425) (1113) (1465) MD UT Str. 14445 14347 1257415110 12934 15609 psi (MPa) (100) (99) (87) (104) (89) (108) TD UT Str.13369 12124 10785 12278 11727 11482 psi (MPa) (92) (84) (74) (85) (81)(79) U Elong. % 285 293 246 296 253 299 U. Elon. % 317 393 305 377 340377 Haze % 59.6 64.0 57.8 62.0 56.9 60.9 45° Gloss 13.6 10.8 13.4 12.014.9 11.9 MD = Machine Direction, TD = Transverse Direction, UT Str =Ultimate Tensile strength U. Elong = Ultimate Elongation

ESCORENE HD7755.10 is a polyethylene polymer available from ExxonChemical Company, Houston, Tex., having an I₂₁ of 7.5, and MIR of 125,an M_(w) of 180,000, a density of 0.95 g/cc, produced using a dualreactor system.

Example 9

Several drums of granular samples (produced following the polymerizationprocedure above with a molar catalyst ratio (Catalyst A/Catalyst B) of2.3 were tumble mixed with 1000 ppm Irganox™ 1076 and 1500 ppm Irgafos™1068 and 1500 ppm of calcium stearate. This tumble-mixed granluar resinwas pelletized on a 2½″ (6.35 cm) Prodex compounding line at 400° F.(204° C.). Thus prepared pellets were film extruded on a 50 mm Alpineblown film line which is equipped with an extruder with 50 mm singlescrew (18:1 L/D ratio) and 100 mm annular die with 1 mm die gap. Theextrusion conditions were: 400° F. (204° C.) die temperature, outputrate-100 lb/hr (46 kg/hr). A typical set temperature profile was: 380°F./400° F./400° F./400° F./400° F./400° F./410° F./410° F. (193° C./204°C./204° C./204° C./204° C./204° C./210° C./210° C.) forBarrel1/Barrel2/Block adaptor/Bottom adaptor/Verical adaptor/Diebottom/Die middle/Die top. The pellet samples were extruded to produce1.0 mil (25 μm) film sample at the line speed of 92 fpm (48 cm/sec) and0.5 mil (13 μm) film sample at the line speed of 184 fpm (94 cm/sec) atthe blow-up ratio (BUR) of 4.0. For both cases the bubble showedexcellent stability with a typical “necked-in” wine glass shape. The FLH(frost line height) of blown bubble was maintained at 36 inches (91.4cm) and 40 inches (101.6 cm), respectively for 1.0 mil (25 μm) and 0.5mil (12.5 μm) film. The extrusion head pressure and motor load exhibitedslightly higher than ESCORENE™ HD7755.10 (a conventional series reactorproduct of Exxon Chemical Company in Mt Belvue Tex.) at the sameextrusion conditions. The resultant film properties are reported inTable B. All the film samples were conditioned at to 23° C., 50%humidity for 40 hours. Dart impact strength of 0.5 mil (12.5 μm) filmexhibited 380 g, which exceeded that of ESCORENE™ HD7755.10 which showed330 g.

TABLE B Escorene ™ 7755 Polymer B I₂ (g/10 min) 0.08 0.062 I₂₁ (g/10min) 10 10.02 I₂₁/I₂ 134 160.5 Density (g/cc) 0.952 0.9485 Output(lb/hr) (kg/hr)   104 (47)  100 (47) Die rate (lb/hr/in die) ˜8 ˜8 Headpressure psi/MPa 7,200 (50) 7600 (53) Motor Load (amp) 56 61 BUR 4 4 FLH(inch) (cm)  36 (91.4)  40 (101.6)  36 (91.4)  40 (101.6) melt fractureno no no Bubble Stability good good good Take-up (fpm) (m/s)  92 (0.5) 185 (0.9)   92 (0.5)  184 (0.9) Film gauge (mil) (μ)    1 (25)   0.5(12.5)   1 (25)  0.5 (12.5) Dart Impact strength (g) 250 330 290 360Tensile str. (psi) (MPa) MD 8,400 (58) 11,300 (78) 8100 (56) 11400 (79)TD 7,900 (55) 10,400 (72) 7230 (50)  9520 (66) Elongation (%) MD 350 230410 330 TD 570 390 580 410 Elmendorf Tear (g/mil) (g/μ) MD  25 (0.98) 22 (0.87)  24 (0.95)   33 (1.30) TD 142 (5.59)  72 (2.83) 205 (8.07)  171 (2.80) Modulus (psi) (MPa) MD 127,000 (876)  144,000 (993) 131500(907)  135350 (933) TD 146,000 (1007)  169,000 (1165) 160250 (1105) 156300 (1078) MD = machine direction, TD = transverse direction.

Example 10

Following the procedure of Example 9, several drums of granular samples(Polymer C produced following the polymerization procedure above with amolar catalyst ratio of Catalyst A to Catalyst B of 0.732 and Polymer Dproduced following the polymerization procedure above with a molarcatalyst ratio of Catalyst A to Catalyst B of 2.6) were tumble mixedwith 1000 ppm Irganox™ 1076, 1500 ppm of calcium stearate and 1500 ppmIrgafos™ 1068 then pelletized and extruded as described in Example 9.All films were conditioned at 23° C. and 50% humidity for 40 hours. Dartimpact strength of a 0.5 mil (12.5 um) film from both Polymer C andPolymer D exhibited 380 g, which exceeded that of ESCORENE™ HD 7755.10which showed 330 g. The data are reported in Table C.

TABLE C Sample Polymer C Polymer D Escorene 7755 Rxn Temp (° C.) 85 85C₂ (psi) (kPa) 220 (1517) 220 (1517) H₂/C₂ (molar) 0.0014-0.0016 0.00102C₆/C₂ (molar) 0.0075-0.0078 0.00531-0.00586 Mn 14,600 16,400 Mw 309,100298,200 291,500 Mw/Mn 21.2 18.2 15.7 HMW/LMW 53.8/46.2 50.5/49.5 I₂(g/10 min) 0.056 0.049 0.08 I₂₁ (g/10 min) 6.48 6.7 10 MFR (I₂₁/I₂)115.8 138 134 Density (g/cc) 0.9487 0.9461 0.952 Output (lb/hr) (kg/hr)102 (46) 102 (46) 100 (45) Die rate (lb/hr/in die) ˜8 ˜8 10 Head. (psi)(MPa) 8,120 (56) 7,890 (54) 7,230 (50) Motor Load (amp) 64.5 63 59 BUR 44 4 FLH (inch) (cm) 40 (101.6) 40 (101.6) 36 (91.4) 40 (101.6) 36 (91.4)40 (101.6) melt fracture no no no Bubble Stability Fair Good Good GoodGood Good Film gauge (mil) (μm) 1 (25.4) 0.5 (12.7) 1 (25.4) 0.5 (12.7)1 (25.4) 0.5 (12.7) Dart Impact (g) 200 380 200 380 250 330 Tensilestrength MD (psi) (MPa) 10,300 19,900 9,900 15,500 8,400 11,300 (71)(137) (68) (107) (58) (78) TD (psi) (MPa) 7,900 13,800 8,400 14,5007,900 10,400 (55) (95) (58) (100) (55) (72) Elongation (%) MD 320 240290 250 350 230 TD 630 385 610 350 570 390 Elmendorf Tear MD (g/mil)(g/μm) 24 (0.95) 21 (0.83) 36 (1.42) 36 (1.42) 25 (0.98) 22 (0.87) TD(g/mil) (g/μm) 410 (16.1) 87 (3.4) 350 (13.8) 66 (2.6) 142 (5.6) 72(2.8) Modulus MD (kpsi) (MPa) 105 (724) 120 (827) 103 (710) 110 (758)127 (876) 144 (993) TD (psi) (MPa) 128 (883) 126 (869) 129 (889) 114(786) 146 169 (1007) (1165) Alpine line, 2″ screw, 4 inch (10.2 cm) die,40 mil (1016 μm) die gap, 410° F. (210° C.) die set Temp.

In addition to the examples above, other variations on polymerizingusing the catalyst systems described herein include:

1. Compound I could be dissolved in a solvent, preferably toluene toform the desired weight % solution then used in combination with othercatalyst systems.

2. Catalyst A could be used as a 0.50 weight % solution in toluene andCatalyst B could be used as a 0.25 weight % solution in hexane at molarratios of B to A of about 0.7 when the two are activated separately thenmixed together (parallel activation) or at molar ratios of B to A of 2.2to 1.5 when A is activated then B is added (sequential activation).

3. Raising or lowering the reaction temperature to narrow or broaden theMw/Mn, respectively.

4. Changing residence time to affect product properties. Large changescan have significant impact. One to five, preferably four hoursresidence time appears to produce good product properties.

5. Spraying the catalyst into the reactor in such a way as to create aparticle lean zone. A particle lean zone can be created by a 50,000lb/hr flow of cycle gas through 6 inch pipe. The catalyst can beatomized w/a spray nozzel using nitrogen atomizing gas.

6. The activator, preferably MMAO 3A can be used at 7 weight % al inisopentane, hexane or heptane at feed rate sufficient to give an Al/Zrratio of 100 to 300.

7. Catalyst A is mixed on-line with MMAO 3A then Catalyst B is added online, then the mixture is introduced into the reactor.

8. Catalyst A is mixed on-line with MMAO 3A and Catalyst B is mixed online with MMAO 3A thereafter the two activated catalysts are mixedon-line then introduced into the reactor.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. It is within the scope of thisinvention to use two or more Group 15 containing metal compounds withone or more bulky ligand metallocene-type catalyst system and/or one ormore conventional type catalyst system. Accordingly it is not intendedthat the invention be limited thereby.

1. A continuous gas phase polymerization process comprising combining ina single gas phase reactor olefin monomers with a catalyst compositioncomprising an activator, a first catalyst compound comprising a Group15-containing metal compound and a second catalyst compound; wherein theGroup 15-containing metal compound is represented by the formula:

wherein M is a Group 4 metal, each X is independently a leaving group, nis the oxidation state of M, m is the formal charge of the ligandcomprising Y, Z and L, L is a Group 15 element, Y is a Group 15 element,Z is a Group 15 element, R¹ and R² are independently a C₁ to C₂₀hydrocarbon group, or a heteroatom containing group having up to twentycarbon atoms, the heteroatom selected from the group consisting ofsilicon, germanium, tin, lead, and phosphorus; wherein optionally, R¹and R² are interconnected to each other, and/or R⁴ and R⁵ may beinterconnected to each other, R³ is absent, a hydrocarbon group, ahydrogen, a halogen, or a heteroatom containing group, R⁴ and R⁵ areindependently an alkyl group, an aryl group, a substituted aryl group, acyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkylgroup, a substituted cyclic arylalkyl group or a multiple ring system,and R⁶ and R⁷ are independently absent, hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group; wherein a polyolefin isproduced; and wherein the melt index (I₂) of the polyolefin is changedby altering the relative amounts of the first catalyst compound and thesecond catalyst compound.
 2. The process of claim 1, wherein the secondcatalyst compound comprises a bulky ligand metallocene compound, aZiegler-Natta catalyst, a Phillips-type catalyst, a vanadium catalyst,or combinations thereof; wherein the Ziegler-Natta catalyst comprisesMR_(x), where M is a metal from Group 4 to 6, and R is a halogen or ahydrocarbyloxy group, and x is the oxidation state of the metal M;wherein the Phillips-type catalyst comprises CrO₃, chromocene, silylchromate, chromyl chloride (CrO₂Cl₂), chromium-2-ethyl-hexanoate, orchromium acetylacetonate (Cr(AcAc)₃); and wherein the vanadium catalystcomprises vanadyl trihalide, alkoxy halides and alkoxides, vanadiumtetra-halide and vanadium alkoxy halides, vanadium or vanadyl acetylacetonates.
 3. The process of claim 1, wherein R⁴ and R⁵ are representedby the formula:

wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, or a heteroatom containing groupcontaining up to 40 carbon atoms wherein any two R⁸⁻¹² groups may form acyclic group or a heterocyclic group.
 4. The process of claim 1, whereinthe second catalyst compound comprises a bulky ligand metallocenecompound of the general formulaL^(D)MQ₂(YZ)X_(n) wherein M is a Group 4, 5 or 6 metal atom, L^(D) is acyclopentadienyl ligand that is bonded to M, Q₂(YZ) forms a unichargedpolydentate ligand, wherein Q is selected from the group consisting of—O—, —NR—, —CR²— and —S—; Y is C; Z is selected from the groupconsisting of —OR, —NR², —CR³, —SR, —SiR³, —PR², —H, and substituted orunsubstituted aryl groups, with the proviso that when Q is —NR— then Zis selected from one of the group consisting of —OR, —NR², —SR, —SiR³,—PR² and —H; R is a hydrocarbon group containing from 1 to 20 carbonatoms; X is a univalent anionic group or a divalent anionic group, and nis 1 or
 2. 5. The process of claim 1, wherein the second catalystcompound comprises a bulky ligand metallocene compound of the generalformula:L^(A)L^(B)MQ_(n) or L^(A)AL^(B)MQ_(n) wherein M is a Group 4, 5 or 6metal atom; L^(A) and L^(B) are selected from the group consisting ofcyclopentadienyl, tetrahydroindenyl, indenyl, fluorenyl, and substitutedversions thereof; Q is a monoanionic leaving group; A is a divalentbridging group containing at least one Group 13 to Group 16 atom; and nis 0, 1 or
 2. 6. The process of claim 3, wherein R⁹, R¹⁰ and R¹² areindependently a methyl, ethyl, propyl or butyl group.
 7. The process ofclaim 3, wherein R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ arehydrogen.
 8. The process of claim 1, wherein M is a Group 4 metal, L, Y,and Z are independently nitrogen, R¹ and R² are a hydrocarbon radical,R³ is hydrogen, and R⁶ and R⁷ are absent.
 9. The process of claim 4,wherein M is a Group 4 metal and L^(D) is an indenyl group or afluorenyl group.
 10. The process of claim 1, wherein the Group15-containing metal compound to the second catalyst system are presentin a molar ratio of 20:80 to 80:20.
 11. The process of claim 1, whereinthe activator is selected from the group consisting of an alumoxane, amodified alumoxane, non-coordinating ionic activators, non-coordinatingneutral activators, and combinations thereof.
 12. The process of claim1, wherein the process is conducted at a temperature of from 30° C. to120° C.
 13. The process of claim 1, wherein the olefins consist ofethylene and at least one comonomer having from 4 to 8 carbon atoms. 14.The process of claim 1, wherein hydrogen from 100 ppm to 5000 ppm isalso combined.
 15. The process of claim 1, wherein the catalystcomposition is introduced into the reactor in a solvent.
 16. The processof claim 1, wherein the catalyst composition also comprises a support.17. The process of claim 13, wherein the process is capable of producinga polyethylene copolymer having a Mw/Mn between 20 and 60, and a densityof between 0.94 to 0.97 g/cm³; wherein the ethylene is copolymerizedwith 1-butene or 1-hexene; wherein the second catalyst compound is abulky ligand metallocene catalyst component and the activator is analumoxane, the Al/Zr molar ratio ranging from 300:1 to 100:1, and themolar ratios of the metals from the first and second catalyst compoundsranges from 30:70 to 70:30.
 18. The process of claim 13, wherein theprocess is capable of producing a polyethylene copolymer having aresidual metal content of 5.0 ppm transition metal or less; wherein theethylene is copolymerized with 1-butene or 1-hexene; wherein the secondcatalyst compound is a bulky ligand metallocene catalyst component. 19.The process of claim 17 or 18, wherein the polyethylene copolymer isformed into a pipe having a notch tensile test value of greater than 500hrs at 3.0 MPa as measured under ASTM F1473.
 20. The process of claim 1,wherein the first catalyst compound and the second catalyst compound andthe activator are mixed off-line and then fed to the reactor.
 21. Theprocess of claim 1, wherein the first catalyst compound and the secondcatalyst compound are mixed off-line, followed by adding the activatorin-line, and then feeding the composition to the reactor.
 22. Theprocess of claim 1, wherein the first catalyst compound is contactedwith the activator off-line, followed by addition of the second catalystcompound in-line before entering the reactor.
 23. The process of claim1, wherein the second catalyst compound is contacted with the activatoroff-line, followed by addition of the first catalyst compound in-linebefore entering the reactor.
 24. The process of claim 1, wherein thefirst catalyst compound and the second catalyst compound are eachcontacted with the activator off-line, followed by the first catalystcompound and activator and the second catalyst compound and activatorbeing contacted in line before entering the reactor.
 25. The process ofclaim 1, wherein the first catalyst compound and the second catalystcompound are each contacted with the activator in-line, followed by thefirst catalyst compound and activator and the second catalyst compoundand activator being contacted in-line before entering the reactor. 26.The process of claim 1, wherein the first catalyst compound is activatedwith activator off-line, followed by the first catalyst compound andactivator being contacted in-line with the second catalyst compound,followed by feeding an activator in-line to the first and secondcatalyst compound activator mixture.
 27. A continuous gas phasepolymerization process comprising combining in at least onepolymerization reactor olefin monomers with a catalyst compositioncomprising an activator, a first catalyst compound comprising a Group15-containing metal compound and a second catalyst compound; wherein theGroup 15-containing metal compound is represented by the formula:

wherein M is a Group 4 metal, each X is independently a leaving group, nis the oxidation state of M, m is the formal charge of the ligandcomprising Y, Z and L, L is a Group 15 element, Y is a Group 15 element,Z is a Group 15 element, R¹ and R² are independently a C₁ to C₂₀hydrocarbon group, or a heteroatom containing group having up to twentycarbon atoms, the heteroatom selected from the group consisting ofsilicon, germanium, tin, lead, and phosphorus; wherein optionally, R¹and R² are interconnected to each other, and/or R⁴ and R⁵ may beinterconnected to each other, R³ is absent, a hydrocarbon group, ahydrogen, a halogen, or a heteroatom containing group, R⁴ and R⁵ areindependently an alkyl group, an aryl group, a substituted aryl group, acyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkylgroup, a substituted cyclic arylalkyl group or a multiple ring system,and R⁶ and R⁷ are independently absent, hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group; wherein a polyolefin isproduced; and wherein the melt index (I₂) of the polyolefin is changedby altering the relative amounts of the first catalyst compound and thesecond catalyst compound.
 28. The process of claim 27, wherein thesecond catalyst compound comprises a bulky ligand metallocene compound,a Ziegler-Natta catalyst, a Phillips-type catalyst, a vanadium catalyst,or combinations thereof; wherein the Ziegler-Natta catalyst comprisesMR_(x), where M is a metal from Group 4 to 6, and R is a halogen or ahydrocarbyloxy group, and x is the oxidation state of the metal M;wherein the Phillips-type catalyst comprises CrO₃, chromocene, silylchromate, chromyl chloride (CrO₂Cl₂), chromium-2-ethyl-hexanoate, orchromium acetylacetonate (Cr(AcAc)₃); and wherein the vanadium catalystcomprises vanadyl trihalide, alkoxy halides and alkoxides, vanadiumtetra-halide and vanadium alkoxy halides, vanadium or vanadyl acetylacetonates.
 29. The process of claim 27, wherein R⁴ and R⁵ arerepresented by the formula:

wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, or a heteroatom containing groupcontaining up to 40 carbon atoms wherein any two R⁸⁻¹² groups may form acyclic group or a heterocyclic group.
 30. The process of claim 27,wherein the second catalyst compound comprises a bulky ligandmetallocene compound of the general formulaL^(D)MQ₂(YZ)X_(n) wherein M is a Group 4,5 or 6 metal atom, L^(D) is acyclopentadienyl ligand that is bonded to M, Q₂(YZ) forms a unichargedpolydentate ligand, wherein Q is selected from the group consisting of—O—, —NR—, —CR²— and —S—; Y is C; Z is selected from the groupconsisting of —OR, —NR², —CR³, —SR, —SiR³, —PR², —H, and substituted orunsubstituted aryl groups, with the proviso that when Q is —NR— then Zis selected from one of the group consisting of —OR, —NR², —SR, —SiR³,—PR² and —H; R is a hydrocarbon group containing from 1 to 20 carbonatoms; X is a univalent anionic group or a divalent anionic group, and nis 1 or
 2. 31. The process of claim 27, wherein the second catalystcompound comprises a bulky ligand metallocene compound of the generalformula:L^(A)L^(B)MQ_(n) or L^(A)AL^(B)MQ_(n) wherein M is a Group 4, 5 or 6metal atom; L^(A) and L^(B) are selected from the group consisting ofcyclopentadienyl, tetrahydroindenyl, indenyl, fluorenyl, and substitutedversions thereof; Q is a monoanionic leaving group; A is a divalentbridging group containing at least one Group 13 to Group 16 atom; and nis 0, 1 or
 2. 32. The process of claim 27, wherein the activator isselected from the group consisting of an alumoxane, a modifiedalumoxane, non-coordinating ionic activators, non-coordinating neutralactivators, and combinations thereof.
 33. The process of claim 27,wherein the olefins consist of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms.
 34. The process of claim 27, whereinthe catalyst composition also comprises a support.
 35. The process ofclaim 27, wherein the process is capable of producing a polyethylenecopolymer having an I₂₁/I₂ of 80 or more, and a density of between 0.94to 0.97 g/cm^(3.)
 36. The process of claim 35, wherein the process iscapable of producing a polyethylene copolymer having an I₂₁/I₂ of 100 ormore.
 37. The process of claim 35, wherein the polyethylene copolymer isformed into a pipe having a notch tensile test value of greater than 500hrs at 3.0 MPa as measured under ASTM F1473.
 38. The process of claim27, wherein the process is capable of producing a polyethylene copolymerhaving an I₂₁ of from 2 to 50 dg/min; wherein the polyethylene copolymeris formed into a film, the film characterized in that a film of 0.5 muformed from such polyethylene copolymer possesses an MD Tear of between20 g/mil and 25 g/mil.
 39. The process of claim 27, wherein the firstcatalyst compound and the second catalyst compound and the activator aremixed off-line and then fed to the reactor.
 40. The process of claim 27,wherein the first catalyst compound and the second catalyst compound aremixed off-line, followed by adding the activator in-line, and thenfeeding the composition to the reactor.
 41. The process of claim 27,wherein the first catalyst compound is contacted with the activatoroff-line, followed by addition of the second catalyst compound in-linebefore entering the reactor.
 42. The process of claim 27, wherein thesecond catalyst compound is contacted with the activator off-line,followed by addition of the first catalyst compound in-line beforeentering the reactor.
 43. The process of claim 27, wherein the firstcatalyst compound and the second catalyst compound are each contactedwith the activator off-line, followed by the first catalyst compound andactivator and the second catalyst compound and activator being contactedin line before entering the reactor.
 44. The process of claim 27,wherein the first catalyst compound and the second catalyst compound areeach contacted with the activator in-line, followed by the firstcatalyst compound and activator and the second catalyst compound andactivator being contacted in-line before entering the reactor.
 45. Theprocess of claim 27, wherein the first catalyst compound is activatedwith activator off-line, followed by the first catalyst compound andactivator being contacted in-line with the second catalyst compound,followed by feeding an activator in-line to the first and secondcatalyst compound activator mixture.
 46. The process of claim 27,wherein the catalyst composition is sprayed into the reactor in such away as to create a particle lean zone, the particle lean zone created bya 50,000 lb/hr flow of cycle gas through 6 inch pipe into the reactor.